US10886560B2 - All-solid-state lithium secondary battery containing LLZO solid electrolyte and method for preparing same - Google Patents
All-solid-state lithium secondary battery containing LLZO solid electrolyte and method for preparing same Download PDFInfo
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- US10886560B2 US10886560B2 US16/072,571 US201616072571A US10886560B2 US 10886560 B2 US10886560 B2 US 10886560B2 US 201616072571 A US201616072571 A US 201616072571A US 10886560 B2 US10886560 B2 US 10886560B2
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- llzo
- conductive polymer
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- solid electrolyte
- secondary battery
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 105
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 93
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 10
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 87
- 239000002131 composite material Substances 0.000 claims abstract description 77
- 238000004519 manufacturing process Methods 0.000 claims abstract description 57
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 37
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 37
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 65
- 239000006182 cathode active material Substances 0.000 claims description 25
- 239000004020 conductor Substances 0.000 claims description 19
- 238000002844 melting Methods 0.000 claims description 19
- 230000008018 melting Effects 0.000 claims description 19
- -1 polysiloxane Polymers 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 17
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 14
- 229910018060 Ni-Co-Mn Inorganic materials 0.000 claims description 8
- 229910018209 Ni—Co—Mn Inorganic materials 0.000 claims description 8
- 229910021450 lithium metal oxide Inorganic materials 0.000 claims description 8
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 239000002223 garnet Substances 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 229910000552 LiCF3SO3 Inorganic materials 0.000 claims description 3
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 239000003273 ketjen black Substances 0.000 claims description 3
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 3
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 3
- 229920002627 poly(phosphazenes) Polymers 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 abstract description 8
- 239000003792 electrolyte Substances 0.000 abstract description 7
- 239000002245 particle Substances 0.000 abstract description 6
- 239000011149 active material Substances 0.000 abstract description 5
- 238000010406 interfacial reaction Methods 0.000 abstract description 5
- 238000005245 sintering Methods 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 description 55
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- 238000005259 measurement Methods 0.000 description 15
- 239000000203 mixture Substances 0.000 description 13
- 239000011230 binding agent Substances 0.000 description 11
- 230000001965 increasing effect Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 239000006245 Carbon black Super-P Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 230000033116 oxidation-reduction process Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000002203 sulfidic glass Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004695 Polyether sulfone Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920006393 polyether sulfone Polymers 0.000 description 2
- 239000011112 polyethylene naphthalate Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910018039 Cu2V2O7 Inorganic materials 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 229910017354 Fe2(MoO4)3 Inorganic materials 0.000 description 1
- 229910020851 La(NO3)3.6H2O Inorganic materials 0.000 description 1
- 229910006570 Li1+xMn2-xO4 Inorganic materials 0.000 description 1
- 229910006628 Li1+xMn2−xO4 Inorganic materials 0.000 description 1
- 229910010228 Li2Mn3MO8 Inorganic materials 0.000 description 1
- 229910010603 Li6.25La3Zr2Al0.25O12 Inorganic materials 0.000 description 1
- 229910010521 LiFe3O4 Inorganic materials 0.000 description 1
- 229910014172 LiMn2-xMxO2 Inorganic materials 0.000 description 1
- 229910014774 LiMn2O3 Inorganic materials 0.000 description 1
- 229910014437 LiMn2−XMXO2 Inorganic materials 0.000 description 1
- 229910002993 LiMnO2 Inorganic materials 0.000 description 1
- 229910014713 LiMnO3 Inorganic materials 0.000 description 1
- 229910014114 LiNi1-xMxO2 Inorganic materials 0.000 description 1
- 229910014907 LiNi1−xMxO2 Inorganic materials 0.000 description 1
- 229910012970 LiV3O8 Inorganic materials 0.000 description 1
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910008337 ZrO(NO3)2.2H2O Inorganic materials 0.000 description 1
- QDDVNKWVBSLTMB-UHFFFAOYSA-N [Cu]=O.[Li] Chemical compound [Cu]=O.[Li] QDDVNKWVBSLTMB-UHFFFAOYSA-N 0.000 description 1
- NRJJZXGPUXHHTC-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] Chemical compound [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] NRJJZXGPUXHHTC-UHFFFAOYSA-N 0.000 description 1
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003013 cathode binding agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- VROAXDSNYPAOBJ-UHFFFAOYSA-N lithium;oxido(oxo)nickel Chemical compound [Li+].[O-][Ni]=O VROAXDSNYPAOBJ-UHFFFAOYSA-N 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
- H01M2300/0091—Composites in the form of mixtures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to an all-solid-state lithium secondary battery containing an LLZO solid electrolyte and a method of manufacturing the same. More particularly, the present invention relates to an all-solid-state lithium secondary battery containing an LLZO solid electrolyte, in which both a cathode and a composite solid electrolyte layer contain a conductive polymer, a lithium salt and an inorganic ceramic solid electrolyte, and to a method of manufacturing the same.
- lithium secondary batteries have large electrochemical capacity, high operating potential and excellent charge/discharge cycle characteristics, there is increasing demand thereof for applications such as portable information terminals, portable electronic devices, small-sized power storage devices for home use, motorcycles, electric vehicles, hybrid electric vehicles, etc. Due to the spread of such applications, improved safety and increasingly high performance of lithium secondary batteries are required.
- An all-solid-state secondary battery is receiving attention as a next-generation secondary battery with the goals of improved safety, high energy density, high power output, long life, simplification of manufacturing processes, formation of large/compact batteries, and reduced costs.
- the key technology of the all-solid-state secondary battery is to develop a solid electrolyte that exhibits high ionic conductivity.
- a solid electrolyte for an all-solid-state secondary battery known to date include a sulfide solid electrolyte and an oxide solid electrolyte.
- Korean Patent Application Publication No. 2012-0132533 discloses an all-solid-state lithium secondary battery having superior power output characteristics using a sulfide-based solid electrolyte as an electrolyte.
- the sulfide solid electrolyte is problematic in that hydrogen sulfide (H 2 S) gas, which is toxic, is generated.
- An oxide solid electrolyte exhibits low ionic conductivity compared to a sulfide solid electrolyte, but is receiving attention these days because of the high stability thereof.
- a conventional oxide-based solid electrolyte results in increased internal resistance of the battery due to an interfacial reaction between an electrolyte and an electrode, thus deteriorating cell discharge capacity and cycle characteristics, which is undesirable.
- the present invention is intended to provide an all-solid-state lithium secondary battery, in which both a cathode and a composite solid electrolyte layer contain a conductive polymer, a lithium salt and an inorganic ceramic solid electrolyte (LLZO), thus improving discharge capacity and cycle characteristics.
- a cathode and a composite solid electrolyte layer contain a conductive polymer, a lithium salt and an inorganic ceramic solid electrolyte (LLZO), thus improving discharge capacity and cycle characteristics.
- LLZO inorganic ceramic solid electrolyte
- the present invention is intended to provide a method of manufacturing an all-solid-state lithium secondary battery, in which the all-solid-state lithium secondary battery including a cathode and a composite solid electrolyte layer, both of which contain a conductive polymer, a lithium salt and an inorganic ceramic solid electrolyte, is manufactured in a non-sintering manner, thus reducing manufacturing costs and controlling interfacial reactions between active materials, between solid electrolyte particles, and between an electrolyte and an electrode, thereby further reducing the internal resistance of the battery.
- an aspect of the present invention provides an all-solid-state lithium secondary battery, comprising: a cathode containing a cathode active material, a first LLZO, a first conductive polymer, a first lithium salt and a conductive material; an anode containing lithium metal; and a composite solid electrolyte layer disposed between the cathode and the anode and configured to contain a second LLZO, a second conductive polymer and a second lithium salt, wherein the first LLZO and the second LLZO are each independently aluminum-doped LLZO or aluminum-undoped LLZO, the undoped LLZO is represented by Chemical Formula 1 below, and the doped LLZO is represented by Chemical Formula 2 below.
- the first LLZO and the second LLZO may each be independently aluminum-doped LLZO.
- the aluminum-doped LLZO may have a garnet crystal structure.
- the cathode may include, based on 100 parts by weight of the cathode active material, 5 to 50 parts by weight of the first LLZO, 5 to 25 parts by weight of the first conductive polymer, and 5 to 25 parts by weight of the conductive material
- the composite solid electrolyte layer may include, based on 100 parts by weight of the second LLZO, 1 to 300 parts by weight of the conductive polymer.
- the first conductive polymer and the second conductive polymer may each independently include at least one selected from the group consisting of polyethylene oxide, polyethylene glycol, polypropylene oxide, polyphosphazene, polysiloxane and copolymers thereof.
- Each of the first conductive polymer and the second conductive polymer may independently be polyethylene oxide having an average molecular weight of 500 to 1000,000.
- the cathode active material may be a Ni—Co—Mn ternary lithium metal oxide (NMC) represented by Chemical Formula 3 below. LiNi p Co q Mn r O 2 [Chemical Formula 3]
- the conductive material may include at least one conductive carbon selected from among carbon black, acetylene black, and KETJENBLACK by AKZO-NOBEL.
- Each of the first lithium salt and the second lithium salt may independently be at least one selected from among lithium perchlorate (LiClO 4 ), lithium triflate (LiCF 3 SO 3 ), lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), and lithium trifluoromethanesulfonyl imide (LiN(CF 3 SO 2 ) 2 ).
- the all-solid-state lithium secondary battery may include a cathode containing aluminum-doped LLZO, polyethylene oxide, a Ni—Co—Mn ternary lithium metal oxide (NMC), lithium perchlorate (LiClO 4 ) and carbon black, an anode containing lithium metal, and a composite solid electrolyte layer disposed between the cathode and the anode and configured to contain aluminum-doped LLZO, polyethylene oxide and lithium perchlorate (LiClO 4 ).
- Another aspect of the present invention provides a method of manufacturing an all-solid-state lithium secondary battery, comprising: (a) manufacturing a cathode containing a cathode active material, a first LLZO, a first conductive polymer, a first lithium salt and a conductive material; (b) manufacturing a composite solid electrolyte layer containing a second LLZO, a second conductive polymer and a second lithium salt; (c) manufacturing a stack by stacking the cathode and the composite solid electrolyte layer; and (d) disposing an anode containing lithium metal on the composite solid electrolyte layer of the stack.
- step (c) may be performed in a manner in which the cathode and the composite solid electrolyte layer are stacked and pressurized at a pressure of 0.1 to 1.0 MPa in a temperature range (T) of Expression 1 below, thus manufacturing the stack.
- T m ⁇ T ⁇ T m +50° C.
- T m T m1 when T m1 >T m2
- T m T m2 when T m1 ⁇ T m2
- T m1 is a melting temperature of the first conductive polymer and T m2 is a melting temperature of the second conductive polymer.
- the first conductive polymer and the second conductive polymer may be polyethylene oxide, and step (c) may be performed in a manner in which the cathode and the composite solid electrolyte layer are stacked and pressurized at a pressure of 0.1 to 1.0 MPa at a temperature of 65° C. (the melting temperature of polyethylene oxide) to 115° C., thus manufacturing the stack.
- the method of manufacturing the all-solid-state lithium secondary battery may further include pressurizing the product of step (d) at a pressure of 0.1 to 1.0 MPa in a temperature range (T) of Expression 1 below. T m ⁇ T ⁇ T m +50° C. [Expression 1]
- T m T m1 when T m1 >T m2
- T m T m2 when T m1 ⁇ T m2
- T m1 is a melting temperature of the first conductive polymer and T m2 is a melting temperature of the second conductive polymer.
- Step (a) may be performed in a manner in which the cathode active material, the LLZO, the first conductive polymer, the first lithium salt and the conductive material are mixed to give a slurry, and the slurry is cast and then dried, thus manufacturing the cathode.
- Still another aspect of the present invention provides a method of manufacturing an all-solid-state lithium secondary battery, comprising: (a′) manufacturing a cathode containing a cathode active material, a first LLZO, a first conductive polymer, a first lithium salt and a conductive material; (b′) manufacturing a composite solid electrolyte layer containing a second LLZO, a second conductive polymer and a second lithium salt; (c′) manufacturing a stack by disposing the cathode, the composite solid electrolyte layer on the cathode, and an anode containing lithium metal on the composite solid electrolyte layer; and (d′) manufacturing an all-solid-state lithium secondary battery by pressurizing the stack at a pressure of 0.1 to 1.0 MPa in a temperature range (T) of Expression 1 below. T m ⁇ T ⁇ T m +50° C. [Expression 1]
- T m T m1 when T m1 >T m2
- T m T m2 when T m1 ⁇ T m2
- T m1 is a melting temperature of the first conductive polymer and T m2 is a melting temperature of the second conductive polymer.
- an all-solid-state lithium secondary battery according to the present invention is configured such that both a cathode and a composite solid electrolyte layer contain a conductive polymer, a lithium salt and an inorganic ceramic solid electrolyte, thus improving the discharge capacity and cycle characteristics of the battery.
- the all-solid-state lithium secondary battery including a cathode and a composite solid electrolyte layer, both of which contain a conductive polymer, a lithium salt and an inorganic ceramic solid electrolyte, is manufactured in a non-sintering manner, thus reducing manufacturing costs and controlling interfacial reactions between active materials, between solid electrolyte particles, and between an electrolyte and an electrode, thereby further reducing the internal resistance of the battery.
- FIG. 1 schematically shows an all-solid-state lithium secondary battery according to the present invention
- FIG. 2 shows the results of measurement of charge/discharge characteristics of all-solid-state lithium secondary batteries of Example 1 and Comparative Example 1;
- FIG. 3 shows the results of measurement of the discharge capacity of the all-solid-state lithium secondary battery of Example 1 upon cycling at 55° C.
- FIG. 4 shows the results of measurement of charge/discharge characteristics of the all-solid-state lithium secondary batteries of Examples 1 and 2 at 70° C.
- FIG. 5 shows the results of measurement of impedance of composite solid electrolyte layers of Preparation Examples 2 to 5 and a polyethylene oxide film of Preparation Example 6;
- FIG. 6 shows the results of measurement of oxidation-reduction behavior of electrochemical cells using the polyethylene oxide film of Preparation Example 6 and the composite solid electrolyte layer of Preparation Example 4;
- FIG. 7 shows the results of measurement of the discharge capacity of coin cells using the composite solid electrolyte layers of Preparation Examples 2 to 5 and the polyethylene oxide film of Preparation Example 6.
- FIG. 1 schematically shows an all-solid-state lithium secondary battery according to the present invention, which is exemplarily configured such that a first conductive polymer and a second conductive polymer are PEO, a cathode active material is a Ni—Co—Mn ternary lithium metal oxide (NMC), and an aluminum current collector and a lithium metal anode are stacked, but the present invention is not limited thereto.
- a first conductive polymer and a second conductive polymer are PEO
- a cathode active material is a Ni—Co—Mn ternary lithium metal oxide (NMC)
- NMC Ni—Co—Mn ternary lithium metal oxide
- FIG. 1 is merely set forth to illustrate but is not to be construed as limiting the present invention, and the present invention will be defined by the accompanying claims.
- the all-solid-state lithium secondary battery may include a cathode containing a cathode active material, a first LLZO, a first conductive polymer, a first lithium salt and a conductive material, an anode containing lithium metal, and a composite solid electrolyte layer disposed between the cathode and the anode and configured to contain a second LLZO, a second conductive polymer and a second lithium salt.
- Each of the first and second LLZOs may independently be aluminum-doped or aluminum-undoped LLZO, and the undoped LLZO may be represented by Chemical Formula 1 below, and the doped LLZO may be represented by Chemical Formula 2 below.
- Li x La y Zr z O 12 (6 ⁇ x ⁇ 9, 2 ⁇ y ⁇ 4, 1 ⁇ z ⁇ 3)
- Li x La y Zr z Al w O 12 (5 ⁇ x ⁇ 9, 2 ⁇ y ⁇ 4, 1 ⁇ z ⁇ 3,0 ⁇ w ⁇ 1) [Chemical Formula 2]
- the first and second LLZOs are aluminum-doped LLZO, and the aluminum-doped LLZO has a garnet crystal structure.
- the garnet crystal structure exhibits high ionic conductivity and superior potential stability.
- the cathode may include 100 parts by weight of a cathode active material, 5 to 50 parts by weight of a first LLZO, 5 to 25 parts by weight of a first conductive polymer, and 5 to 25 parts by weight of a conductive material.
- the first conductive polymer is preferably contained in an amount of 5 to 30 parts by weight based on 100 parts by weight of the cathode active material, and more preferably, the first conductive polymer is contained in an amount of 10 to 20 parts by weight based on 100 parts by weight of the cathode active material.
- the cycle characteristics of the all-solid-state lithium secondary battery may be improved depending on the amount of the cathode active material contained in the cathode, and preferably, the first LLZO is contained in an amount of 10 to 40 parts by weight based on 100 parts by weight of the cathode active material.
- the composite solid electrolyte layer may include 1 to 300 parts by weight of the second conductive polymer based on 100 parts by weight of the second LLZO, preferably 1 to 280 parts by weight of the second conductive polymer based on 100 parts by weight of the second LLZO, and more preferably, 1 to 250 parts by weight of the second conductive polymer based on 100 parts by weight of the second LLZO.
- Each of the first conductive polymer and the second conductive polymer may independently include polyethylene oxide, polyethylene glycol, polypropylene oxide, polyphosphazene, polysiloxane and copolymers thereof.
- polyethylene oxide having an average molecular weight of 500 to 1,000,000, more preferably polyethylene oxide having an average molecular weight of 1,000 to 400,000, and even more preferably polyethylene oxide having an average molecular weight of 5,000 to 300,000 is used.
- Both the cathode and the composite solid electrolyte layer contain the LLZO and the conductive polymer, thus enhancing interfacial properties between active material particles, between solid electrolyte particles, and between an electrolyte layer and an electrode, thereby improving the discharge capacity and cycle characteristics of the all-solid-state lithium secondary battery.
- a conductive polymer typically indicates a polymer having conductivity of at least 10 ⁇ 7 Scm ⁇ 1 (equal to or greater than that of a semiconductor), and in most cases, a polymer is doped with an electron acceptor or an electron donor to thus obtain high conductivity.
- the doped polyethylene, polypyrrole, polythiophene, and the like are known to be typical conductive polymers.
- the choice of a conductive polymer that may be complexed with a lithium salt to attain optimal ionic conductivity is preferable, and polyethylene oxide is preferably used.
- the cathode active material may include, but are not limited to, at least one transition metal-substituted compound or a lamellar compound, such as lithium cobalt oxide (LiCoO 2 ), lithium nickel oxide (LiNiO 2 ), etc.; lithium manganese oxide represented by Li 1+x Mn 2-x O 4 (wherein x is 0 to 0.33), such as LiMnO 3 , LiMn 2 O 3 , LiMnO 2 , etc.; lithium copper oxide (Li 2 CuO 2 ); vanadium oxide, such as LiV 3 O 8 , LiFe 3 O 4 , V 2 O 5 , Cu 2 V 2 O 7 , etc.; Ni site-type lithium nickel oxide represented by LiNi 1-x M x O 2 (wherein M is Co, Mn, Al, Cu, Fe, Mg, B or Ga, and x is 0.01 to 0.3); lithium manganese composite oxide represented by LiMn 2-x M x O 2 (wherein M is Co, Ni
- the cathode active material is preferably a Ni—Co—Mn ternary lithium metal oxide (NMC) represented by Chemical Formula 3 below. LiNi p Co q Mn r O 2 [Chemical Formula 3]
- the conductive material may include carbon black, acetylene black, KETJENBLACK by AKZO-NOBEL, and the like, and is preferably carbon black.
- the first lithium salt and the second lithium salt are each independently lithium perchlorate (LiClO 4 ), lithium triflate (LiCF 3 SO 3 ), lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium trifluoromethanesulfonyl imide (LiN(CF 3 SO 2 ) 2 ), and the like, and are preferably lithium perchlorate.
- the all-solid-state lithium secondary battery preferably includes a cathode containing aluminum-doped LLZO, polyethylene oxide, Ni—Co—Mn ternary lithium metal oxide (NMC), lithium perchlorate (LiClO 4 ) and carbon black; an anode containing lithium metal; and a composite solid electrolyte layer disposed between the cathode and the anode and configured to contain aluminum-doped LLZO, polyethylene oxide and lithium perchlorate (LiClO 4 ).
- a cathode containing a cathode active material, a first LLZO, a first conductive polymer, a first lithium salt and a conductive material is manufactured (step a).
- a slurry containing the cathode active material, the first LLZO, the first conductive polymer, the first lithium salt and the conductive material, which are mixed together, is cast and then dried, thus manufacturing a cathode.
- step b a composite solid electrolyte layer containing a second LLZO, a second conductive polymer and a second lithium salt is manufactured.
- a substrate is coated with a composite solid electrolyte mixture containing the second LLZO, the second conductive polymer and the lithium salt, thus manufacturing a composite solid electrolyte layer.
- the substrate may include PET (polyethylene terephthalate), PEN (polyethylene naphthalate), PES (polyether sulfone), PC (polycarbonate), PP (polypropylene), or the like, and is preferably PET.
- PET polyethylene terephthalate
- PEN polyethylene naphthalate
- PES polyether sulfone
- PC polycarbonate
- PP polypropylene
- the coating process may be performed without limitation, so long as it does not damage the substrate.
- a stack is manufactured by stacking the cathode and the composite solid electrolyte layer (step c).
- the cathode and the composite solid electrolyte layer are stacked and pressurized at a pressure of 0.1 to 1.0 MPa in the temperature range (T) of Expression 1 below, thus manufacturing the stack.
- T m ⁇ T ⁇ T m +50° C.
- T m T m1 when T m1 >T m2
- T m T m2 when T m1 ⁇ T m2
- T m1 is a melting temperature of the first conductive polymer and T m2 is a melting temperature of the second conductive polymer.
- the pressurization process is preferably performed at a pressure of 0.1 to 1.0 MPa, more preferably 0.1 to 0.8 MPa, and still more preferably 0.2 to 0.4 MPa.
- the pressurization process is performed for 5 sec to 5 min, preferably 5 sec to 3 min, and more preferably 5 sec to 1 min.
- the first conductive polymer and the second conductive polymer are preferably polyethylene oxide.
- step (c) may be carried out in a manner in which the cathode and the composite solid electrolyte layer are stacked and pressurized at a pressure of 0.1 to 1.0 MPa at a temperature of 65 to 115° C., thus manufacturing the stack.
- the pressurization is performed at a temperature equal to or higher than the melting temperature of the first conductive polymer and the second conductive polymer, whereby the first conductive polymer contained in the cathode and the second conductive polymer contained in the composite solid electrolyte layer are melted and then adhered to each other, thus improving the interfacial properties between the cathode and the composite solid electrolyte layer to thereby reduce the internal resistance of the battery.
- an all-solid-state lithium secondary battery is manufactured by disposing an anode containing lithium metal on the composite solid electrolyte layer of the stack (step d).
- step (d) pressurizing the product of step (d) at a pressure of 0.1 to 1.0 MPa in the temperature range (T) of Expression 1 may optionally be further performed.
- the first conductive polymer contained in the cathode and the second conductive polymer contained in the composite solid electrolyte layer may be melted and then adhered to each other, and thus the resulting effects are as described in step (c).
- a method of manufacturing an all-solid-state lithium secondary battery may include (a′) manufacturing a cathode containing a cathode active material, a first LLZO, a first conductive polymer, a first lithium salt and a conductive material; (b′) manufacturing a composite solid electrolyte layer containing a second LLZO, a second conductive polymer and a second lithium salt; (c′) manufacturing a stack by disposing the cathode, the composite solid electrolyte layer on the cathode, and an anode containing lithium metal on the composite solid electrolyte layer; and (d′) manufacturing an all-solid-state lithium secondary battery by pressurizing the stack at a pressure of 0.1 to 1.0 MPa in the temperature range (T) of Expression 1.
- the first conductive polymer contained in the cathode and the second conductive polymer contained in the composite solid electrolyte layer may be melted and then adhered to each other, and thus the resulting effects are as described in step (c).
- lanthanum nitrate La(NO 3 ) 3 .6H 2 O
- zirconium nitrate ZrO(NO 3 ) 2 .2H 2 O
- aluminum nitrate Al(NO 3 ) 3 .9H 2 O
- the starting material solution, 0.6 mol of ammonia water as a complexing agent, and an appropriate amount of sodium hydroxide aqueous solution were added via the inlet of a Couette-Taylor vortex reactor, thus obtaining a mixed solution having a pH of 11, which was then subjected to coprecipitation at a reaction temperature of 25° C. for 4 hr at a stirring rate of the stirring rod of 1,300 rpm to give a precursor slurry in a liquid slurry phase, which was then discharged through the outlet thereof.
- the Taylor number in the coprecipitation reaction of the Couette-Taylor vortex reactor was 640 or more.
- the precursor slurry was washed with purified water and dried overnight.
- the dried precursor was pulverized using a ball mill, added with an excess of LiOH.H 2 O, and mixed together using a ball mill, thus preparing a mixture.
- LiOH.H 2 O of the mixture was added in an amount in excess of 3 wt % so that the Li content of LiOH.H 2 O was 103 parts by weight based on 100 parts by weight of Li of the produced solid electrolyte.
- the mixture was calcined at 900° C. for 2 hr and then pulverized, thereby yielding aluminum-doped LLZO (Al-LLZO), Li 6.25 La 3 Zr 2 Al 0.25 O 12 .
- Al-LLZO and a polyethylene oxide (PEO) solid electrolyte binder were weighed such that the amount of Al-LLZO was 30 wt % based on the total weight (Al-LLZO+PEO) of Al-LLZO of Preparation Example 1 and PEO (average molecular weight: 200,000, melting temperature: 65° C.), and were then stirred at 2,000 rpm for 5 min using a Thinky mixer, thus preparing a mixture.
- PEO polyethylene oxide
- the PEO solid electrolyte binder was a mixed solution including PEO, ACN and LiClO 4 , and the amount of PEO was 25 wt % based on the total weight of the PEO solid electrolyte binder. Also, the PEO solid electrolyte binder was designed to have ionic conductivity, and the content ratio of PEO and LiClO 4 ([EO][Li]) was 15:1.
- the mixture was mixed with ACN, and stirred using a Thinky mixer, and thus the viscosity thereof was adjusted to a proper level. Thereafter, the resulting mixture was added with zirconia balls having a size of 2 mm and stirred for 5 min at 2,000 rpm using a Thinky mixer, thus preparing a slurry.
- the slurry was cast on a PET (polyethylene terephthalate) film and dried at room temperature, thereby manufacturing a composite solid electrolyte layer having a thickness of 80 ⁇ m.
- a composite solid electrolyte layer was manufactured in the same manner as in Preparation Example 2, with the exception that the amount of Al-LLZO was 50 wt % based on the total weight (Al-LLZO+PEO) of Al-LLZO of Preparation Example 1 and polyethylene oxide.
- a composite solid electrolyte layer was manufactured in the same manner as in Preparation Example 2, with the exception that the amount of Al-LLZO was 70 wt % based on the total weight (Al-LLZO+PEO) of Al-LLZO of Preparation Example 1 and polyethylene oxide.
- a composite solid electrolyte layer was manufactured in the same manner as in Preparation Example 2, with the exception that the amount of Al-LLZO was 90 wt % based on the total weight (Al-LLZO+PEO) of Al-LLZO of Preparation Example 1 and polyethylene oxide.
- a polyethylene oxide film was manufactured in the same manner as in Preparation Example 2, with the exception that the Al-LLZO of Preparation Example 1 was not added.
- a cathode active material lithium nickel cobalt manganese oxide, NMC
- a conductive material Super-P
- a PEO binder and Al-LLZO of Preparation Example 1 were mixed at a weight ratio of 70:10:10:10 (wt %).
- the PEO binder was a mixed solution including PEO (Polyethylene Oxide, average molecular weight: 200,000, melting temperature: 65° C.), ACN and LiClO 4 , and the amount of PEO was 25 wt % based on the total weight of the PEO binder. Also, the PEO binder was designed to have ionic conductivity, and the content ratio of PEO and LiClO 4 ([EO]:[Li]) was 15:1.
- NMC, Super-P and Al-LLZO of Preparation Example 1 were weighed at the above weight ratio and mixed for 30 min using a mortar and pestle, thus preparing a mixed powder.
- the mixed powder was placed in a vessel for a Thinky mixer and the PEO binder was also added thereto at the above weight ratio, after which the vessel was placed in the mixer, followed by mixing three times for 5 min at 2,000 rpm, thus preparing a mixture. Thereafter, the mixture was added with ACN (acetonitrile) to obtain appropriate viscosity, and was then added with zirconia balls and mixed at 2,000 rpm for 5 min, thus preparing a slurry. Finally, the slurry was cast on a piece of aluminum foil and dried in a vacuum oven at 60° C. for 24 hr, thereby manufacturing a cathode. The dry thickness thereof was adjusted to about 35 ⁇ m.
- a cathode was manufactured in the same manner as in Preparation Example 3, with the exception that the mixing weight ratio of NMC:Super-P:PEO binder:Al-LLZO was set to 60:10:10:20 instead of 70:10:10:10, which is the mixing weight ratio of NMC:Super-P:PEO binder:Al-LLZO.
- NMC, Super-P and an 8% PVDF (poly-1,1-difluoroethene) solution were weighed at a weight ratio (wt %) of 80:10:10 based on the solid content thereof and were then mixed to give a mixture.
- the mixture was stirred at 2,000 rpm for 5 min using a Thinky mixer, added with NMP (n-methyl-2-pyrrolidone), and further stirred using a Thinky mixer to obtain appropriate viscosity. Thereafter, the resulting mixture was added with zirconia balls having a size of 2 mm and stirred at 2,000 rpm for 5 min using a Thinky mixer, thus preparing a slurry.
- the slurry was cast on a piece of aluminum foil using a glass rod and then dried in an oven at 110° C. for 24 hr, thereby manufacturing a cathode. The dry thickness thereof was adjusted to about 15 ⁇ m.
- the cathode of Preparation Example 7 and the composite solid electrolyte layer of Preparation Example 4 were punched at a size of ⁇ 16 and then stacked. Next, heating at about 70 to 80° C. and pressurization at a pressure of 0.3 MPa for about 10 sec were performed, thus manufacturing a stack. Lithium metal was placed on the stack, thereby manufacturing an all-solid-state lithium secondary battery as a 2032 coin cell.
- An all-solid-state lithium secondary battery was manufactured in the same manner as in Example 1, with the exception that the cathode of Preparation Example 8 was used in lieu of the cathode of Preparation Example 7.
- An all-solid-state lithium secondary battery was manufactured in the same manner as in Example 1, with the exception that the cathode of Preparation Example 9 was used in lieu of the cathode of Preparation Example 7.
- FIG. 2( a ) shows the charge/discharge characteristics of the all-solid-state lithium secondary battery of Example 1 measured at 55° C. with current of 0.1 C
- FIG. 2( b ) shows the charge/discharge characteristics of the all-solid-state lithium secondary battery of Comparative Example 1 measured at 70° C. with current of 0.1 C.
- the all-solid-state lithium secondary battery of Example 1 exhibited an initial discharge capacity of about 130 mAh/g or more at 55° C. and maintained a discharge capacity of about 83% at 45 cycles.
- the all-solid-state lithium secondary battery of Comparative Example 1 was reduced in cycle capacity compared to the all-solid-state lithium secondary battery of Example 1.
- the all-solid-state lithium secondary battery of Example 1 including the cathode containing the conductive polymer PEO and the solid electrolyte LLZO, was greatly improved in cycle characteristics compared to the all-solid-state lithium secondary battery of Comparative Example 1, which included the cathode containing PVDF.
- Test Example 2 Measurement of Discharge Capacity Upon Cycling
- FIG. 3 shows the results of measurement of discharge capacity of the all-solid-state lithium secondary battery of Example 1 upon cycling at 55° C.
- the all-solid-state lithium secondary battery of Example 1 maintained a discharge capacity of about 83% at 45 cycles.
- the all-solid-state lithium secondary battery of Example 1 was found to have superior discharge capacity.
- FIG. 4( a ) shows the charge/discharge characteristics of the all-solid-state lithium secondary battery of Example 1 measured at 70° C. with current of 0.1 C
- FIG. 4( b ) shows the charge/discharge characteristics of the all-solid-state lithium secondary battery of Example 2 measured at 70° C. with current of 0.1 C.
- the all-solid-state lithium secondary battery of Example 1 exhibited a slightly increased initial discharge capacity at 70° C. compared to 55° C. and maintained a discharge capacity of 85% at 30 cycles. Also, the all-solid-state lithium secondary battery of Example 2 exhibited a superior initial discharge capacity of about 150 mAh/g, but a reduction in the capacity thereof was increased with an increase in the number of charge/discharge cycles.
- the all-solid-state lithium secondary battery of Example 1 slowed the degradation of an all-solid-state lithium secondary battery even at a high temperature of 70° C., and was superior in initial discharge capacity and cycle characteristics compared to 55° C. Furthermore, the cycle characteristics thereof were further improved compared to the all-solid-state lithium secondary battery of Example 2.
- FIG. 5 shows the results of calculation of ionic conductivity from impedance measured under conditions of 7 MHz-100 mHz and 5 mV after mounting of a SUS jig with each of the composite solid electrolyte layers of Preparation Examples 2 to 5 and the polyethylene oxide film of Preparation Example 6 at room temperature.
- the polyethylene oxide film of Preparation Example 6, containing no LLZO exhibited an ionic conductivity of 2.68 ⁇ 10 ⁇ 7 S/cm.
- the amount of Al-LLZO in the composite solid electrolyte layers of Preparation Examples 2 to 5 was increased to 30, 50, 70, and 90 wt %, the conductivity values were increased to 7.9 ⁇ 10 ⁇ 7 , 4.83 ⁇ 10 ⁇ 6 , 7.59 ⁇ 10 ⁇ 6 , and 3.43 ⁇ 10 ⁇ 5 S/cm, respectively.
- the ionic conductivity of the composite solid electrolyte layer was increased with an increase in the amount of Al-LLZO.
- FIG. 6 shows the results of measurement of oxidation-reduction behavior in electrochemical cells using the polyethylene oxide film of Preparation Example 6 and the composite solid electrolyte layer of Preparation Example 4.
- electrochemical cells using the polyethylene oxide film and the composite solid electrolyte layer were manufactured and subjected to cyclic voltammetry.
- the operating electrode of the electrochemical cells was made of SUS, and the counter electrode was made of lithium metal.
- the electrochemical cells using the polyethylene oxide film of Preparation Example 6 and the composite solid electrolyte layer of Preparation Example 4 exhibited safe electrochemical reactivity up to about 5V.
- the polymer decomposition oxidation potential was further shifted in the (+) direction, and thus, when the amount of Al-LLZO that was added was increased, the electrochemical potential window was further increased.
- Test Example 6 Measurement of Discharge Capacity of Coin Cell Depending on PEO/LLZO Amount of Composite Solid Electrolyte Layer
- FIG. 7 shows the results of measurement of the discharge capacity of coin cells using the composite solid electrolyte layers of Preparation Examples 2 to 5 and the polyethylene oxide film of Preparation Example 6.
- the capacity was increased with an increase in the amount of Al-LLZO of the composite solid electrolyte layer, and the cycle characteristics were also improved.
- the characteristics of the coin cell using the composite solid electrolyte layer (70 wt % of Al-LLZO) of Preparation Example 4 were superior, which is deemed to be because the interfacial control of the coin cell using the composite solid electrolyte layer of Preparation Example 4 is excellent.
- the formation of the composite solid electrolyte layer such that the amount of Al-LLZO is 70 wt % based on the total weight (Al-LLZO+PEO) of Al-LLZO and polyethylene oxide can be found to be preferable.
- an all-solid-state lithium secondary battery according to the present invention is configured such that both a cathode and a composite solid electrolyte layer contain a conductive polymer, a lithium salt and an inorganic ceramic solid electrolyte, thus improving discharge capacity and cycle characteristics.
- the all-solid-state lithium secondary battery including a cathode and a composite solid electrolyte layer, both of which contain a conductive polymer, a lithium salt and an inorganic ceramic solid electrolyte, is manufactured in a non-sintering manner, thus reducing manufacturing costs and controlling interfacial reactions between active materials, between solid electrolyte particles, and between an electrolyte and an electrode, thereby further reducing the internal resistance of the battery.
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Abstract
Description
LixLayZrzO12(6≤x≤9, 2≤y≤4, 1≤z≤3) [Chemical Formula 1]
LixLayZrzAlwO12(5≤x≤9, 2≤y≤4, 1≤z≤3, 0<w≤1) [Chemical Formula 2]
LiNipCoqMnrO2 [Chemical Formula 3]
T m ≤T≤T m+50° C. [Expression 1]
T m ≤T≤T m+50° C. [Expression 1]
T m ≤T≤T m+50° C. [Expression 1]
LixLayZrzO12(6≤x≤9, 2≤y≤4, 1≤z≤3) [Chemical Formula 1]
LixLayZrzAlwO12(5≤x≤9, 2≤y≤4, 1≤z≤3,0<w≤1) [Chemical Formula 2]
LiNipCoqMnrO2 [Chemical Formula 3]
T m ≤T≤T m+50° C. [Expression 1]
Claims (14)
LixLayZr7O12 (6≤x≤9, 2≤y≤4,1≤z≤3)
LixLayZr7AlwO12 (5≤x≤9, 2≤y≤4, 1≤z≤3, 0<w≤1) and
LiNipCoqMnrO2,
T m ≤T≤T≤ m+50° C.,
T m ≤T≤T m+50° C. [Expression 1]
T m ≤T≤T m+50° C.,
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PCT/KR2016/013120 WO2017135553A1 (en) | 2016-02-03 | 2016-11-15 | All-solid-state lithium secondary battery containing llzo solid electrolyte and method for preparing same |
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US12006387B1 (en) | 2022-11-14 | 2024-06-11 | Piersica, Inc. | Polymer composition and methods for making same |
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US20200280093A1 (en) * | 2017-11-07 | 2020-09-03 | The Regents Of The University Of Michigan | Solid-State Battery Electrolyte Having Increased Stability Towards Cathode Materials |
KR102016916B1 (en) | 2017-12-26 | 2019-09-02 | 한국화학연구원 | Method for producing LLZO oxide solid electrolyte powder |
KR102012431B1 (en) * | 2018-02-14 | 2019-08-20 | 한국생산기술연구원 | Anode for all solid lithium secondary battery, method for manufacturing the same, and all solid lithium secondary battery comprising the same |
KR102016622B1 (en) * | 2018-02-21 | 2019-08-30 | 한국생산기술연구원 | All solid lithium secondary battery having improved electric potential stability and method for manufacturing the same |
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